Ionic polyimides (i-PI) are a new class of polymer materials that are very promising for CO2 capture membranes, and recent experimental studies have demonstrated their enhanced separation performance with the addition of imidazolium-based ionic liquids (ILs). However, there is very little known about the molecular-level interactions in these systems, which give rise to interesting gas adsorption and diffusion characteristics. In this study, we use a combination of Monte Carlo and molecular dynamics simulations to analyze the equilibrium and transport properties of CO2 molecules in the i-PI and i-PI + IL composite materials. The addition of several different common ILs are modeled, which have a plasticization effect on the i-PI, lowering the glass transition temperature (Tg). The solubility of CO2 strongly correlates with the Tg, but the diffusion demonstrates more unpredictable behavior. At low concentrations, the IL has a blocking effect, leading to reduced diffusion rates. However, as the IL surpasses a threshold value, the relationship is inverted and the IL has a facilitating effect on the gas transport. This behavior is attributed to the simultaneous contributions of the increased i-PI plasticization at higher IL concentrations (facilitating gas hopping rates from cavity-to-cavity) and the increased IL continuity throughout the system, enabling more favorable transport pathways for CO2 diffusion.